EP0784636B1 - Particules de polymeres agglomerees constituees de polymerisats finement divises, renfermant des groupes carboxylate d'ammonium, solubles dans l'eau ou susceptibles de gonflement dans l'eau - Google Patents
Particules de polymeres agglomerees constituees de polymerisats finement divises, renfermant des groupes carboxylate d'ammonium, solubles dans l'eau ou susceptibles de gonflement dans l'eau Download PDFInfo
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- EP0784636B1 EP0784636B1 EP95934108A EP95934108A EP0784636B1 EP 0784636 B1 EP0784636 B1 EP 0784636B1 EP 95934108 A EP95934108 A EP 95934108A EP 95934108 A EP95934108 A EP 95934108A EP 0784636 B1 EP0784636 B1 EP 0784636B1
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- Prior art keywords
- water
- monoethylenically unsaturated
- mol
- polymerized
- polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/18—Increasing the size of the dispersed particles
Definitions
- GB-A-1 319 632 describes a process for the production of granular polymers known, in which one first Water-in-oil emulsion of a water-soluble monomer in one produces organic solvents, the emulsion being ethyl cellulose or polyvinyl acetate and a water soluble emulsifier from a condensation product of ethylene oxide or Propylene oxide and alcohols, amines, amides, fatty acids or Contains phenols.
- the water-in-oil emulsion is then in Polymerized in the presence of initiators and then by dewatered azeotropic distillation.
- the granular polymer is filtered off. It has a particle size of approx. 1 to 6 mm. Such coarse-particle polymers dissolve very slowly Water.
- the agglomerated polymer particles disintegrate into an aqueous medium into the primary particles.
- the azeotropic Dehydration of polymers containing ammonium carboxylate groups contain, however, difficulties arise because depending on the duration evaporate various amounts of ammonia along with the to a non-reproducible degree of hydrolysis of the polymer leads. As a result, the polymer lies quantitatively on the boiler wall of the discharge boiler until the stirrer gets stuck.
- the present invention is therefore based on the object agglomerated polymer particles from finely divided, water-soluble or containing water-swellable ammonium carboxylate groups
- Polymers and a process for their preparation are available to deliver.
- the polymers are said to have a narrow particle size distribution have, the maximum of the particle size distribution by changing the manufacturing process conditions can be varied easily.
- the carboxylic acids optionally partially or completely neutralized with ammonia Form present, according to the known method of water-in-oil polymerization polymerize or if such water-in-oil polymer emulsions are available, directly assume and the emulsions in the presence of the agglomerating polyalkylene glycols and the protective colloids to be used according to the invention dewater azeotropically.
- polymerization uses the free carboxylic acids, there is an at least partial Neutralization with ammonia or amines of the copolymers before azeotropic drainage.
- Water-soluble monoethylenically unsaturated carboxylic acids are suitable as monomers. They can be used in the form of the free acids or preferably in a form partially or completely neutralized with ammonia or amines. Examples of these monomers are monoethylenically unsaturated C 3 to C 6 carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and ethacrylic acid. From this group of monomers, preference is given to using acrylic acid, methacrylic acid or mixtures of acrylic acid and methacrylic acid in any ratio.
- the last-mentioned monomers are preferably used in the polymerization with methylenebisacrylamide as crosslinking agent, the carboxylic acids optionally being present in a form partially or completely neutralized with ammonia.
- the monomers are preferably neutralized in an aqueous medium with ammonia or amines such as methylamine, ethylamine, n-propylamine, isopropylamine, butylamine, morpholine, monoethanolamine, diethanolamine or triethanolamine.
- the monoethylenically unsaturated carboxylic acids can be copolymerized either alone or as a mixture with other monoethylenically unsaturated monomers to form water-soluble copolymers.
- Such monomer mixtures contain at least 50% by weight of a monoethylenically unsaturated carboxylic acid.
- Suitable other monoethylenically unsaturated monomers are water-soluble monomers such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, acrylamidomethylpropanesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, vinyl lactic acid, N-vinylpyrrolidone, vinylimidazole, 2-vinylimidazolate, N-vinylformamide, hydroxyethyl methyl acrylate, hydroxyethyl methyl acrylate and N-methylol methacrylamide.
- water-soluble monomers such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, acrylamidomethylpropanesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, vinyl lactic acid, N-vinylpyrrolidone, vinylimidazole, 2-vinylimidazolate, N-vinylformamide, hydroxyethyl methyl acrylate, hydroxy
- monoethylenically unsaturated monomers which can optionally be copolymerized with the monoethylenically unsaturated carboxylic acids to give water-soluble copolymers, are described in WO-A-92/13912.
- the other monoethylenically unsaturated monomers are preferably used in amounts of up to 50% by weight in the monomer mixture.
- the monoethylenically unsaturated carboxylic acids can optionally also be copolymerized with water-insoluble monomers, the water-insoluble monomers then being used in such an amount that the resulting copolymers are still soluble in water or that the copolymers in the form of the ammonium salts are soluble in water.
- Water-insoluble monomers are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, C 1 to C 18 alkyl esters of monoethylenically unsaturated C 3 to C 6 carboxylic acids, for example methyl acrylate, ethyl acrylate, octyl acrylate, palmityl acrylate, stearyl acrylate, methyl methacrylate and palmethyl methacrylate, ethyl methacrylate.
- mixtures of acrylic acid and acrylamide and / or methacrylamide or mixtures of methacrylic acid and acrylamide and / or methacrylamide are preferably used as water-soluble monomers and methylene bisacrylamide is used as the crosslinking agent.
- crosslinking agents are connections that have at least two ethylenically unsaturated non-conjugated double bonds in the Contain molecule.
- Suitable crosslinkers are, for example, N, N'-methylenebisacrylamide, Polyethylene glycol diacrylates and polyethylene glycol dimethacrylates, each of which is composed of polyethylene glycols of a molecular weight derived from 106 to 8,500, trimethylolpropane triacrylate, Trimethylolpropane trimethacrylate, ethylene glycol diacrylate, Propylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, Hexanediol dimethacrylate, diacrylates and dimethacrylates of block copolymers from ethylene oxide and propylene oxide, twice or addition products triple esterified with acrylic acid or methacrylic acid of ethylene oxide and / or propylene oxide on trimethylolpropane, at least twice with acrylic acid or methacrylic acid esterified polyhydric alcohols, such as glycerin or Pentaerythritol, triallylamine, t
- Triallylmethylammonium chloride Preferably you bet water soluble crosslinkers, e.g. N, N'-methylene-bisacrylamide, Polyethylene glycol diacrylates, polyethylene glycol dimethacrylates, Pentaerythritol triallyl ether and / or divinyl urea.
- the Crosslinkers are used, for example, in an amount of 50 to 5000 ppm corresponding to about 0.003 to 0.3 mol%, based on the monomers used in the polymerization.
- the monomers are first dissolved in Water.
- the concentration of the monomers in the aqueous solution is e.g. 20 to 80, preferably 30 to 60 wt .-%.
- the aqueous solution is then formed to form a water-in-oil emulsion in an inert hydrophobic liquid (oil phase) in Presence of at least one water-in-oil emulsifier.
- Inert hydrophobic liquids can practically all be mixed with water immiscible liquids are used that are not in the Intervene polymerization. This is preferably used aliphatic and aromatic hydrocarbons or mixtures from aliphatic and aromatic hydrocarbons.
- Suitable aliphatic hydrocarbons are, for example, pentane, Hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, Decalin, isooctane and ethylcyclohexane.
- Aromatic hydrocarbons that as a hydrophobic liquid in reverse suspension polymerization are used, for example Benzene, toluene, xylene and isopropylbenzene.
- halogenated hydrocarbons such as Tetrachloroethane, hexachloroethane, trichloroethane and chlorobenzene use.
- Cyclohexane and methylcyclohexane are preferably used or hydrocarbons with a boiling range of 60 to 170 ° C.
- the proportion of the oil phase in the build-up of the water-in-oil polymer emulsion is 15 to 70, preferably 20 to 60 wt .-%.
- the water-in-oil emulsifiers in question have one HLB value of at most 8.
- the HLB value is understood to be the hydrophilic-lipophilic Balance of the emulsifier, cf. WC. Griffin, J. Soc. Cosmet. Chem. Volume 1, 411 (1949).
- the water-in-oil emulsifiers are, based on the monomers used, in a Amount of 2 to 20, preferably 5 to 15 wt .-% used.
- Preferably water-in-oil emulsifiers are used, which are described in said DE-B-2 557 324.
- Polymerization initiators which form free radicals can be used all polymerization initiators commonly used be used.
- Water-soluble initiators such as Alkali or ammonium peroxydisulfates, hydrogen peroxide, Diacetyl peroxidicarbonate, dicyclohexyl peroxidicarbonate, tert-butyl perpivalate, Dilauroyl peroxide, dibenzoyl peroxide, tert-butyl per-2-ethylhexanoate, tert-butyl permaleinate, bis (tert-butyl peroxide) cyclohexane, tert-butyl peracetate, dicumyl peroxide, di-tert-amyl peroxide, Di-tert-butyl peroxide, cumyl hydroperoxide, tert-butyl hydroperoxide and p-menthane hydroperoxide and azo initiators, such as 2,2'-azobis (2-methyl-N-phenylpro
- Preferred Initiators are alkali and ammonium persulfates, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-amidinopropane) dihydrochloride, Azobis (isobutyronitrile) and 2,2'-azo-bis [2 (2-imidazolin-2-yl) propane] dihydrochloride.
- Such mixtures of initiators enable polymerizing at lower temperatures.
- the reducing component of so-called redox initiators can for example of sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate or hydrazine are formed.
- Related to the monomers used in the polymerization are required e.g. 100 to 10,000, preferably 100 to 2000 ppm of one Polymerization initiator or a mixture of several polymerization initiators.
- the specified amounts of initiator correspond about 0.003 to 0.3 mol% of initiator, based on the used Monomers.
- the polymerization of the water-soluble monomers is additionally carried out in the presence of at least one oil-in-water emulsifier.
- This group of emulsifiers enables the production of particularly fine-particle, sedimentation-stable water-in-oil polymer emulsions.
- the average particle size of such polymer emulsions is in the range from, for example, 0.1 to 15 ⁇ m, determined by Fraunhofer diffraction, cf. HG Barth, Modern Methods of Partial Size Analysis, John Wiley & Sons, New York, 1984.
- Suitable oil-in-water emulsifiers are, for example, all wetting agents which have an HLB value of at least 10.
- This group of emulsifiers are essentially hydrophilic water-soluble compounds, such as ethoxylated alkylphenols or ethoxylated fatty alcohols. Products of this kind are obtained for example by reacting C 8 - to C 12 -alkylphenols or C 8 - to C 22 fatty alcohols reacted with ethylene oxide. C 12 -C 18 fatty alcohols are preferably ethoxylated. The molar ratio of alkylphenol or fatty alcohol to ethylene oxide is generally 1: 5 to 1:20.
- Other suitable emulsifiers are, for example, alkoxylated fatty amines. If emulsifiers with an HLB value of 10 or above are used in the polymerization, they are used, for example, in amounts of 1 to 20, preferably 2 to 15,% by weight, based on the monomers to be polymerized.
- the monomers are polymerized in the aqueous phase a water-in-oil emulsion in the presence of water-in-oil emulsifiers and optionally oil-in-water emulsifiers and in the presence of Radical polymerization initiators.
- the available The polymers contain water-in-oil polymer emulsions in the form of primary particles with average particle sizes of 0.1 to 15 ⁇ m, preferably 0.5 to 5 ⁇ m. At least 90% of the Primary particles of the water-in-oil polymer emulsion have a medium one Particle diameter of ⁇ 10 ⁇ m.
- the polymerization of the monomers can optionally in the presence of polymerization regulators to determine the molecular weight of the polymers to limit.
- Suitable regulators are, for example Compounds containing SH groups such as dodecyl mercaptan, thioglycol, Mercaptoethanol, mercaptopropanol, mercaptobutanols, Mercaptoacetic acid and mercaptopropionic acid. More suitable Regulators are carbon tetrachloride, hydroxylammonium sulfate, Formic acid and its salts, alcohols such as e.g. Methanol, isopropanol or butylene glycol. In case of polymerization uses a regulator, it is used in quantities from 0.1 to 5%, based on the monomers.
- the water-soluble copolymers have K values from 150 to 300 (determined according to H. Fikentscher in 0.5% aqueous solution pH 7 and 25 ° C).
- the K values of the polymers were determined according to H. Fikentscher, Cellulose-Chemie, Volume 93, 58 to 64 and 71 to 74 (1932).
- the high molecular weight polymers are preferred as a flocculant in the dewatering of sewage sludge or used in papermaking.
- the polyalkylene glycols act during azeotropic drainage agglomeration of the water-in-oil polymer emulsions the primary particles of the water-in-oil polymer emulsion.
- azeotropic drainage are agglomerations of primary particles which, according to sieve analysis, has an average particle diameter from 20 to 2500, preferably 30 to 500 microns. That in the Water contained in water-in-oil emulsion polymers is caused by azeotropic distillation at least 70%, preferably 80 to 99% removed. Small amounts of water in the polymers remain, do not disturb, on the contrary, they lead to the fact that dissolve the agglomerated particles in water faster than completely dried agglomerated particles.
- Water-in-oil polymer emulsions that have a solids content of have more than 20 wt .-%, are expediently before the start azeotropic distillation with 10 to 200 wt .-%, preferably with 50 to 150% by weight of a hydrocarbon with a boiling point offset below 150 ° C.
- the azeotropic dewatering of the water-in-oil polymer emulsion can at normal pressure or under reduced Pressure and optionally under increased pressure e.g. in the range from 100 mbar to 15 bar.
- the temperatures are preferably chosen so that the water-in-oil polymer emulsions, which are drained, if possible not damaged will. Usually the water-in-oil polymer emulsions to a temperature in the range of 60 to 170 ° C heated.
- the polyalkylene glycols which are suitable as agglomeration aids are available, for example, in that the alkylene oxides in question, these are ethylene oxide, Propylene oxide, 1,2-butylene oxide and isobutylene oxide or tetrahydrofuran attached to alcohols, phenols, amines or carboxylic acids.
- the mentioned alkylene oxides and tetrahydrofuran can either alone or polymerized in a mixture. If mixtures are used are obtained, polymeric compounds in which the Alkylene oxide units are statistically distributed. However, one can also the alkylene oxides in the usual way to block copolymers let it react. Homopolymers of ethylene oxide are, for example obtained by adding ethylene oxide to ethylene glycol.
- Block copolymers are produced, for example, by that you first add ethylene oxide to ethylene glycol and react and then propylene oxide under the usual conditions, i.e. by catalysis with alkali hydroxides or calcium oxide, attaches. There are many ways to order them here to vary the blocks of alkylene oxide units. For example A propylene oxide block can be attached to an ethylene oxide block and then connect an ethylene oxide block.
- Polyalkylene glycols can be used as agglomeration aids an ethylene oxide, a propylene oxide block and a butylene oxide block have or polyalkylene glycols, in which on one Propylene oxide block followed by an ethylene oxide block or such polyalkylene oxides where on a butylene oxide block a propylene oxide block and optionally an ethylene oxide block follows.
- the end groups of the resulting polyalkylene glycols can be closed on one side or on both sides.
- Polyalkylene glycols sealed on one side are obtained, for example, by adding alkylene oxides to alcohols, phenols, amines or carboxylic acids.
- Suitable alcohols are, for example, monohydric C 1 to C 22 alcohols, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-octanol, isooctanol and stearyl alcohol.
- Polyhydric alcohols can also be used as alcohols, for example, as already mentioned above, ethylene glycols or propylene glycols, and also glycerol, pentaerythritol and 1,6-hexanediol.
- the alkylene oxides can also be added to phenol and substituted phenols, such as C 1 - to C 18 -alkylphenols.
- Amines are also suitable as end group closures, for example C 1 -C 18 -alkyl- or dialkylamines and diamines, preferably ethylenediamine.
- Of particular interest here are commercially available products which can be obtained, for example, by sequential addition of ethylene oxide and propylene oxide onto ethylenediamine.
- Thioalcohols such as mercaptoethanol, mercaptopropanols and mercaptobutanols can also be alkoxylated.
- the terminal OH groups of the polyalkylene glycols can also be replaced, for example, by amino groups.
- Polyalkylene glycols whose terminal OH groups are etherified or esterified are also suitable as agglomeration aids.
- the polyalkylene glycols in question contain at least 2 alkylene oxide units copolymerized.
- Suitable agglomeration aids are, for example, polyethylene glycols, polypropylene glycols, block copolymers of ethylene oxide and propylene oxide blocks of the structure EO-PO, PO-EO-PO or EO-PO-EO, polyethylene glycols etherified on one or both sides with C 1 -C 4 -alcohols and such compounds , which can be obtained by the addition of first ethylene oxide and then propylene oxide or in reverse order on ethylenediamine.
- Suitable polyalkylene glycols agglomerating include diethylene glycol, triethylene glycol, tetraethylene glycol, pentamethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, Triethylenglykolmono- and dimethyl ether, triethylene glycol mono and diethyl ether, Dialkylenglykoldibutylether, diethylene glycol monobutyl ether, Diethylenglykolmonopropylether, Diethylenglykoldipropylether, EO-PO Block copolymers with average molecular weights from 120 to 2 million, PO-EO-PO block copolymers with average molecular weights from 178 to 2 million and EO-PO-EO block copolymers with average molecular weights from
- Component (b) of the copolymers are monoethylenically unsaturated C 4 to C 8 dicarboxylic acid anhydrides, for example maleic anhydride, itaconic anhydride, mesaconic anhydride, citraconic anhydride, methylene malonic anhydride and mixtures of these anhydrides.
- maleic anhydride is preferably used.
- the copolymers contain 40 to 60 mol% of monoolefins and 60 to 40 mol% of the dicarboxylic acid anhydrides in question and have a molar mass of 500 to 20,000, preferably 800 to 10,000 g / mol.
- Monomers (a) and (b) are obtainable by polymerizing the monomers (a) and (b) in a molar ratio of 1.1: 1 to 1: 1.
- Monomers (a) and (b) are preferably polymerized in a molar ratio of 1: 1 or only a 1% by weight excess of monomers of component (a) is used.
- the monomers of groups (a) and (b) form alternating copolymers which, at high molecular weights, contain the monomers (a) and (b) in copolymerized form in each case at 50 mol%.
- the copolymers obtained in bulk polymerization contain anhydride groups and have molecular weights from 500 to 20,000 g / mol.
- the copolymers containing anhydride groups are preferably used directly in azeotropic drainage. However, one can also contain the anhydride groups First hydrolyze copolymers so that those containing acid groups Copolymers are available that with the same success as Protective colloid can be used. It is also possible the copolymers containing anhydride groups by reaction to modify with alcohols, alkali metal bases, ammonia or amines, so that the derivatives described in EP-A-0 412 389 arise like those containing ester, carboxylate and amide groups Copolymers.
- agglomerated polymer particles After the azeotropic dewatering there are agglomerated polymer particles in a hydrocarbon oil.
- the polymer particles can easily be isolated from it, e.g. by filtering, decanting hydrocarbon oil or by centrifugation.
- Adhered hydrocarbon oil can easily come out of the agglomerated Polymer particles are removed, e.g. by drying in one Drying cabinet, preferably at higher temperatures and below reduced pressure.
- the agglomerated polymer particles preferably consist of partially or completely neutralized with ammonia or amines cross-linked polyacrylic acid, cross-linked polymethacrylic acid, cross-linked copolymers of acrylic acid and methacrylic acid or from crosslinked copolymers of acrylic acid and Acrylamide and / or methacrylamide containing polymerized in Acrylamide and / or methacrylamide from 1 to 20 wt .-% as well crosslinked copolymers of methacrylic acid and acrylamide or methacrylamide containing polymerized amides from 1 to 20% by weight.
- the content of crosslinker in the crosslinked Copolymers is preferably 50 to 2000 ppm, based on the monomers, the preferred crosslinker used Is N, N'-methylenebisacrylamide.
- the agglomerated polymers disintegrate when placed in an aqueous medium, e.g. in a aqueous polymer dispersion or an aqueous textile printing paste quickly into the primary particles.
- the crosslinked polymers swell in water and thereby increase the viscosity of the aqueous Systems.
- water-soluble polymers e.g. high molecular weight Polyacrylic acid dissolve from the agglomerated Primary particles are formed in water.
- the agglomerated crosslinked polymer particles according to the invention used as a thickener for textile pigment printing pastes. The amount of thickener is 0.5 to 5 wt .-%, based on the printing paste.
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Claims (5)
- Particules de polymère agglomérées formées de polymères solubles dans l'eau ou pouvant gonfler dans l'eau et contenant des groupements carboxylate d'ammonium, qui contiennent en liaison polymère au moins 50% en poids d'un acide carboxylique à insaturation monoéthylénique, les particules agglomérées ayant un diamètre moyen de particules de 200-2500µm et formées de particules primaires ayant un diamètre moyen de particules de 0,1-15µm, pouvant être obtenues par polymérisation de mélanges de monomères constitués d'au moins 50% en poids d'acides carboxyliques à insaturation monoéthylénique et éventuellement d'autres monomères à insaturation monoéthylénique et éventuellement d'agents de réticulation, selon le procédé de polymérisation eau-dans-huile, et pouvant être préparées par séchage azéotrope jusqu'à au moins 70% de l'émulsion eau-dans-huile de polymères contenant les particules primaires, en présence de polyalkylèneglycols à action agglomérante qui peuvent être obtenus para) addition d'oxydes d'alkylène en C2-C4 sur des alcools, des phénols, des amines ou des acides carboxyliques, etb) qui contiennent au moins deux motifs oxyde d'alkylène en liaison polymère,a) monooléfines en C8-C40 avecb) des anhydrides d'acides dicarboxyliques en C4-C6 à insaturation monoéthylénique
- Procédé de préparation de particules polymères agglomérées selon la revendication 1 par séchage azéotrope jusqu'à au moins 70% d'émulsions eau-dans-huile de polymères solubles dans l'eau ou pouvant gonfler dans l'eau et contenant des groupements carboxylate d'ammonium, ayant un diamètre moyen de particules de 0,1-15µm, en présence de 0,1-40% en poids, par rapport aux polymères, de polyalkylèneglycols à action agglomérante qui peuvent être obtenus para) addition d'oxydes d'alkylène en C2-C4 sur des alcools, des phénols, des amines ou des acides carboxyliques, etb) qui contiennent au moins deux motifs oxyde d'alkylène en liaison polymère,a) monooléfines en C8-C40 avecb) des anhydrides d'acides dicarboxyliques en C4-C6 à insaturation monoéthylénique
- Procédé de préparation de particules polymères agglomérées selon la revendication 2, caractérisé en ce que l'on utilise comme monomères solubles dans l'eau, lors de la polymérisation, de l'acide acrylique, de l'acide méthacrylique, des mélanges d'acide acrylique et d'acide méthacrylique, et du méthylènebisacrylamide en tant qu'agent réticulant, les acides carboxyliques se trouvant éventuellement sous forme neutralisée de façon partielle ou totale avec de l'ammoniaque.
- Procédé selon la revendication 2, caractérisé en ce que l'on utilise comme monomères solubles dans l'eau, lors de la copolymérisation, des mélanges d'acide acrylique et d'acrylamide et/ou de méthacrylamide ou des mélanges d'acide méthacrylique et d'acrylamide et/ou de méthacrylamide ainsi que du méthylènebisacrylamide en tant qu'agent réticulant.
- Utilisation des particules polymères selon la revendication 1 en tant qu'agent épaississant pour pâtes d'impression de pigments pour textiles.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE4435425 | 1994-10-04 | ||
DE4435425A DE4435425A1 (de) | 1994-10-04 | 1994-10-04 | Agglomerierte Polymerteilchen aus feinteiligen, wasserlöslichen oder wasserquellbaren Ammoniumcarboxylatgruppen enthaltenden Polymerisaten |
PCT/EP1995/003772 WO1996010589A1 (fr) | 1994-10-04 | 1995-09-23 | Particules de polymeres agglomerees constituees de polymerisats finement divises, renfermant des groupes carboxylate d'ammonium, solubles dans l'eau ou susceptibles de gonflement dans l'eau |
Publications (2)
Publication Number | Publication Date |
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EP0784636A1 EP0784636A1 (fr) | 1997-07-23 |
EP0784636B1 true EP0784636B1 (fr) | 1998-12-02 |
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Application Number | Title | Priority Date | Filing Date |
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EP95934108A Expired - Lifetime EP0784636B1 (fr) | 1994-10-04 | 1995-09-23 | Particules de polymeres agglomerees constituees de polymerisats finement divises, renfermant des groupes carboxylate d'ammonium, solubles dans l'eau ou susceptibles de gonflement dans l'eau |
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US (2) | US6586534B1 (fr) |
EP (1) | EP0784636B1 (fr) |
DE (2) | DE4435425A1 (fr) |
WO (1) | WO1996010589A1 (fr) |
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SE0300726D0 (sv) * | 2003-03-14 | 2003-03-14 | Amersham Biosciences Ab | Method for preparing a separation medium |
WO2005118650A2 (fr) * | 2004-06-04 | 2005-12-15 | Basf Aktiengesellschaft | Procede de marquage de materiaux |
WO2007116554A1 (fr) | 2006-03-31 | 2007-10-18 | Asahi Kasei Chemicals Corporation | Agglomerats de particules de resine hydroabsorbante et leur procede de production |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2982749A (en) * | 1957-07-15 | 1961-05-02 | Dow Chemical Co | Inverse suspension polymerization of water soluble unsaturated monomers |
US3200098A (en) * | 1961-02-28 | 1965-08-10 | Kerr Mc Gee Oil Ind Inc | Polymerization of acrylamide monomer in the presence of free ammonia and the resulting polyacrylamide product |
GB1319632A (en) | 1970-03-18 | 1973-06-06 | Ici Ltd | Process for the preparation of water-soluble polymers in solid form |
JPS58154708A (ja) * | 1982-03-09 | 1983-09-14 | Kyoritsu Yuki Kogyo Kenkyusho:Kk | 高吸水性樹脂の製造方法 |
US4525527A (en) * | 1982-01-25 | 1985-06-25 | American Colloid Company | Production process for highly water absorbable polymer |
US4777231A (en) * | 1987-11-06 | 1988-10-11 | Nalco Chemical Company | Process to produce water absorbent polymers |
DE3926120A1 (de) * | 1989-08-08 | 1991-02-14 | Basf Ag | Verfahren zur herstellung von feinteiligen polymerisatpulvern |
DE4103969A1 (de) | 1991-02-09 | 1992-08-13 | Basf Ag | Verfahren zur herstellung von feinteiligen, wasserloeslichen oder wasserquellbaren polymerisaten |
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1994
- 1994-10-04 DE DE4435425A patent/DE4435425A1/de not_active Withdrawn
-
1995
- 1995-09-23 EP EP95934108A patent/EP0784636B1/fr not_active Expired - Lifetime
- 1995-09-23 WO PCT/EP1995/003772 patent/WO1996010589A1/fr active IP Right Grant
- 1995-09-23 DE DE59504442T patent/DE59504442D1/de not_active Expired - Lifetime
- 1995-09-23 US US08/809,710 patent/US6586534B1/en not_active Expired - Fee Related
-
2002
- 2002-09-19 US US10/246,721 patent/US20030073797A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
US20030073797A1 (en) | 2003-04-17 |
EP0784636A1 (fr) | 1997-07-23 |
WO1996010589A1 (fr) | 1996-04-11 |
US6586534B1 (en) | 2003-07-01 |
DE59504442D1 (de) | 1999-01-14 |
DE4435425A1 (de) | 1996-04-11 |
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